Water-soluble sulfonated phosphorus(v) corrolazines and porphyrazines: the effect of macrocycle contraction and pyrazine ring fusion on spectral, acid-base and photophysical properties

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F22%3A00550871" target="_blank" >RIV/61388955:_____/22:00550871 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11160/22:10450587

Výsledek na webu

<a href="http://hdl.handle.net/11104/0326178" target="_blank" >http://hdl.handle.net/11104/0326178</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d1dt02453a" target="_blank" >10.1039/d1dt02453a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Water-soluble sulfonated phosphorus(v) corrolazines and porphyrazines: the effect of macrocycle contraction and pyrazine ring fusion on spectral, acid-base and photophysical properties

Popis výsledku v původním jazyce

Novel water-soluble dihydroxophosphorus(v) complexes of sulphophenyl substituted porphyrazine (6), corrolazine (7) and its pyrazine fused derivative (8) were prepared and their spectral, acid-base and photophysical properties in aqueous solutions were studied. Due to the presence of eight SO3H groups, the compounds were fully monomeric (7 and 8) or only slightly aggregated (6) in water. Spectrophotometric titration revealed that the two stage deprotonation of axially bonded hydroxy groups can be achieved for porphyrazine 6 (pK(a1) = 5.62, pK(a2) = 9.13) and pyrazine fused corrolazine 8 (pK(a1) = 6.5, pK(a2) = 11.7), while only the first dissociation stage could be observed for corrolazine 7 (pK(a1) = 9.94). The fluorescence emission of the corrolazines 7, 8 and especially porphyrazine 6 was low in water (Phi(F) = 0.086, 0.18, and 0.014, respectively) and completely quenched under basic conditions due to photoinduced electron transfer. In comparison with porphyrazine 6, the contraction of the macrocycle in the corrolazines 7 and 8 induced significant improvement of singlet oxygen production in water reaching values of Phi(Delta) = 0.56 and 0.43, respectively, which makes the corrolazines promising photosensitizers for photodynamic therapy. The observed evolution of the electronic absorption spectra and fluorescence quenching observed in a basic medium was explained using the model DFT calculations (cc-pvtz basis set) performed for the dihydroxophosphorus(v) complexes of unsubstituted porphyrazine and corrolazine and their mono- and doubly deprotonated forms.

Název v anglickém jazyce

Water-soluble sulfonated phosphorus(v) corrolazines and porphyrazines: the effect of macrocycle contraction and pyrazine ring fusion on spectral, acid-base and photophysical properties

Popis výsledku anglicky

Novel water-soluble dihydroxophosphorus(v) complexes of sulphophenyl substituted porphyrazine (6), corrolazine (7) and its pyrazine fused derivative (8) were prepared and their spectral, acid-base and photophysical properties in aqueous solutions were studied. Due to the presence of eight SO3H groups, the compounds were fully monomeric (7 and 8) or only slightly aggregated (6) in water. Spectrophotometric titration revealed that the two stage deprotonation of axially bonded hydroxy groups can be achieved for porphyrazine 6 (pK(a1) = 5.62, pK(a2) = 9.13) and pyrazine fused corrolazine 8 (pK(a1) = 6.5, pK(a2) = 11.7), while only the first dissociation stage could be observed for corrolazine 7 (pK(a1) = 9.94). The fluorescence emission of the corrolazines 7, 8 and especially porphyrazine 6 was low in water (Phi(F) = 0.086, 0.18, and 0.014, respectively) and completely quenched under basic conditions due to photoinduced electron transfer. In comparison with porphyrazine 6, the contraction of the macrocycle in the corrolazines 7 and 8 induced significant improvement of singlet oxygen production in water reaching values of Phi(Delta) = 0.56 and 0.43, respectively, which makes the corrolazines promising photosensitizers for photodynamic therapy. The observed evolution of the electronic absorption spectra and fluorescence quenching observed in a basic medium was explained using the model DFT calculations (cc-pvtz basis set) performed for the dihydroxophosphorus(v) complexes of unsubstituted porphyrazine and corrolazine and their mono- and doubly deprotonated forms.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

51

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

1364-1377

Kód UT WoS článku

000732842800001

EID výsledku v databázi Scopus

2-s2.0-85123799707